Monoazo dyestuffs



United States Patent 3,394,123 MONGAZO DYESTUFFS Karl Ronco, Riehen, and Paul Hegner, Basel, Switzerland,

assignors to Ciba Limited, Basel, Switzerland, a company of Switzerland No Drawing. Continuation-impart of application Ser. No. 309,876, Sept. 18, 1963. This application Feb. 15, 1966, Ser. No. 527,508 Claims priority, application Switzerland, Sept. 8, 1962, 11,430/ 62; Aug. 7, 1963, 9,773/ 63 8 Claims. (Cl. 260-203) This is a continuation-in-part of our copending application Serial No. 309,876 filed September 18, 1963 and now abandoned.

The present invention provides carboxylic acid amide azo dyestulfs free from acidic groups imparting solubility in Water that correspond to the formula in which R, andR, represent phenylene radicals, R represents a naphthalene radical in which the azo, hydroxyl and carboxylic acid amide groups are in 1-, 2- and 3- position respectively, R represents an aryl radical free from aroylamino groups, for example, a pyrene, naphthalene or more especially a benzene radical, and R represents a benzene radical that may be substituted.

Of special interest are dyestuffs of the formula l I Z1 -OH X2 (X3) n-l X --0 ONE NHC o-O in which X represents a hydrogen atom or a halogen atom, or a lower alkoxy group, atom, X, represents a halogen atom or a trifiuoromethyl group, Y and Z represent hydrogen or halogen atoms or trifluoromethyl groups, Z represents a halogen atom or an alkyl group or more especially an alkoxy group, Z represents a hydrogen or halogen atom, X represents a halogen atom or an alkyl group, Y represents a halogen atom or an alkyl or alkoxy group, X represents a halogen atom or an alkyl or alkoxy group or a phenyl group, and n represents an integer from 1 to 4.

The new dyestuffs are obtained when a carboxylic acid halide free from acidic groups imparting solubility in water and corresponding to the formula (3) N=N-R1C ONHRa OH R2 COHal is condensed with a monoamine free from acidic groups imparting solubility in water and corresponding to the formula (4) H NR -NHCOR in which formulae R and R represent phenylene groups, R represents a naphthalene radical in which the azo, hydroxyl and carboxylic acid halide groups are in l-, 2-

3,394,123 Patented July 23, 1968 and 3-position respectively, R represents a benzene or naphthalene radical free from cyclic substituents, and R represents a benzene radical.

The dyestufis used as starting materials in the process of the invention must be free from acidic groups imparting solubility in water, especially sulfonic acid and carhoxylic acid groups.

As azo dyestutf carboxylic acid chlorides there are advantageously used those of the formula r X COC1 Y1 in which X represents a hydrogen or halogen atom, X represents a halogen atom or a trifiuoromethyl group, Y and Z represent hydrogen atoms, halogen atoms or trifiuoromethyl groups, Z represents a halogen atom or an alkyl group or more especially an alkoxy group and Z represents a hydrogen atom or a halogen atom.

The azo dyestufi carboxylic acids from which the acid halides are prepared are obtained when the diazo compound of an aminocarboxylic acid arylide of the formula in which R and R have the meanings given above, are coupled With a 2:3-hydroxynaphthoic acid which may be substituted in the benzene ring free from the carboxylic acid group, for example, by a halogen. atom, especially a bromine atom, in 6-position.

As examples of aminoearboxylic acids of the formula (6) there may be mentioned:

4-chloro-3-aminobenzoic acid-2' 5 '-dichloranilide, 4-chloro-3-aminobenzoic acid-3-chloranilide, 4-ehloro-3-aminobenzoic acid-2'-chloro-5'-trifluoromethylanilide, 4-chloro-3-aminobenzoic acid-3-trifluoromethylani1ide, 4-chloro-3-aminobenzoic acid-3' 5-bis-trifluoromethyla-nilide, 4-chloro-3 -aminobenzoic acid-2' :4 5 -trichloroanilide, 2:4-dichloro-3-aminobenzoic acid-2:S-dichloroanilide, 2:4-dichloro-3-aminoibenzoic acid-3-trifl.uoromethylanilide, 2:4-dichloro-3-aminobenzoic acid-3'-chloroanilide, S-amino-4-rnethoxy-2-chlorobenzoic acid-3'-trifluoromethylanilide, 4-methy-l-3-aminobenzoic acid-2':5-dichloroanilide, 4-methyl-3-aminobenzoic acid-3'-trifluoromethylanilide, 4-methoXy-3-aminobenzoic acid-3'-chloroanilide, 4-methoxy-3-arninobenzoic acid-2':5-dichloroanilide, 4-methoXy-3 -aminoibzenoic acid-2' :4 S'trichloroanilide, 4-methoxy-3-aminobenzoic acid-3-trifluoromethylanilide, 4-methoXy-3-amin0benz0io methylanilide, 4-methoxy-3-aminobenzoic fluoromethylanilide, 4-methoxy-3-aminobenzoic 4-chloroanilide, 4-inethoXy-3-aminobenzoic 4'-chloroanilide, 4-methoxy-3-aminobenzoic acid-u-naphthylamide, 4-methoxy-3-aminobenzoio acid-B-naphthylamide and 4-methoxy-3-amnobenzoic acid-(5: 8'-dichloro)- ot-naphthylamide.

The azocarboxylic acids so obtained are treated with acid-3' 5 -bis-trifluoroacid-2'-chloro-5-triacid-2' 5 '-dimethoxyacid-2' 5 -dinnetl1ylespecially with phosphorus halides such as phosphorus pentabromide or phosphorus trichloride or phosphorus pentachloride, phosphorus oxyhalides, and advantageously thionylchloride.

The treatment with such acid halogenating agents is advantageously carried out in an inert organic solvent such as a chlorobenzene, for example, monoor di-chlorobenzene, toluene, xylene or nitrobenzene, toluene, xylene or nitrobenzene.

In the preparation of the carboxylic acid halides it is generally of advantage first to dry the azocarboxylic acids which are prepared in aqueous 'medium, or to free them from water by azeotropic distillation with an organic solvent. If desired, this azeotropic drying can be carried out immediately prior to the treatment with the acid halogenating agent.

The monoamines to be used in the process of the invention advantageously correspond to the formula 7) X z (Kan-1 in which X and Y have the meanings given above, X represents a halogen atom or an alkyl or a phenyl radical, and n represents an integer not greater than 4. As example there may be mentioned:

4-benzoylamino-aniline, 4-(4-chlorobenzoylamine)-aniline, 2: 5-dichloro-4-benzoylaminoaniline, 2 5 -dichloro-4- (4-chlorobenzoylamino -aniline, 2 5-dichloro-4- 2' 4'-dichloro benzoylamine) -aniline, -dichloro-4- 2' 5 -dichlorobenzoylamino -aniline, -dichloro-4- 4'-methylbenzoylamino -aniline, -dich1oro-4- (4-phenylbenzoylamino -aniline, -dimethyl-4-benzoylamineaniline, -dimethyl-4-(4-chlorobenzoylamino)-aniline, -dimethy1-4-(2 :4-dichlorobenzoylamino -aniline, imethyl-4-(2':5-dichlorobenzoy1amine)-aniline, imethyl-4- (4'-methylbenzoylamino -aniline, -di-methyl-4- (4-phenylbenzoylamino -aniline, 2: 5-dimethy1-4- 4-methoxybenzoylamino -aniline, 2-chloro-5-methyl-4-benzoylaminoaniline, 2-chloro-5-methyl-4- 4'-chlorobenzylamino -aniline, 2-chloro-5-methyl-4- 2' 5 -dichlorobenzoylamine) aniline, 2-chloro-5-methyl-4- 4-methylbenzoylamino) -aniline, 2-chloro-5-methyl-4- 4'-phenylbenzoylamino -aniline, Z-methoxy-S-chloro-4-benzoylaminoani1ine, 2-methoxy-5-chloro-4- 4-chlorobenzoylamino) -aniline, Z-methoxy-S -ch1oro-4- 2 5 -dichlorobenzoylamino aniline, 2-methoxy-5-chloro-4- 4-methylbenzoyla mino aniline and 2-methoxy-5-chloro-4- 4-phenylbenzoylamine) aniline.

The condensation between the carboxylic acid halides defined above and the amines is advantageously carried out in anhydrous medium. Under these conditions the condensation generally proceeds surprisingly easily, even at temperatures within the boiling range of the common organic solvents such as toluene, monochlorobenzene, dichlorobenzene, trichl-orobenzene, nitrobenzene and the like. In order to accelerate the reaction it is generally of advantage to use an agent capable of binding acid, for example, anhydrous sodium acetate or pyridine. Some of the dyestuffs obtained are crystalline and some are amorphous, and they are generally obtained in a very good yield and in pure form. It is advantageous first to isolate the acid chlorides obtained but in some cases, however, this can be omitted without harm, and the condensation can be carried out immediately after the preparation of the carboxylic acid chlorides.

The dyestuffs of the invention can be obtained by a modification of the present process according to which the diazo compound of an amine of the formula N HR CONHR is coupled with a compound of the formula OH R2 in which formulae R ,R ,R ,R and R have the meanings given above. The coupling is advantageously carried out in such a manner that an acid solution of the diazonium salt is continuously added to an alkaline solution of the coupling component in a mixing nozzle whereby immediate coupling of the components takes place. Care should be taken to ensure that the diazo component and the coupling component are present in the mixing nozzle in equimolecular proportions. The simplest method of achieving this is by controlling the pH value of the liquid in the mixing nozzle. Provision should also be made for a vigorous turbulent motion of the two solutions in the mixing nozzle. The resulting dyestuff dispersion is removed continuously from the mixing nozzle and the dyestuff is separated by filtration.

In a further modification of the present process, the new dyestuffs are obtained by coupling the diazo compuund of an amine of the formula 8 H N-R CONHR with a compound of the formula Cum OH R2 in which R represents a hydrogen atom or an alkyl radical and R represents an alkyl radical or the radicals R and R form a heterocyclic ring together with the nitrogen atom. As examples there may be mentioned the radicals of methylamine, dimethylamine, diethylamine, diethanolamine, pyrrolidine, piperidine and morpholine. The compounds of the formula (9) can be obtained by reacting compounds of the formula C ONII NIIC 0- in which R X Y X and n have the meanings given above, with formaldehyde and a primary or secondary amine.

The radical CH A is split off during coupling and is replaced by the azo group. Coupling is advantageously carried out in an acid medium.

The new dyestuffs are valuable pigments that can be used for a wide variety of purposes, for example, they can be used in a finely divided form for the spin dyeing of rayon and viscose, cellulose ethers or esters, poly amides, polyurethanes or polyesters; for the manufacture of colored lacquers or lakes; for coloring solutions or products of cellulose acetate, nitrocellulose, natural or synthetic resins such as polymerization or condensation resins, for example, aminoplasts, alkyd resins, phenoplasts, polyolefines such as polystyrene, polyvinyl A mixture comprising 10.7 parts of the chloride so obtained, 5.3 parts of 2:5-dimethyl-4-benzoylaminoaniline and 300 parts of orthodichlorobenzene was heated for 14 hours at 140 to 145 C. The crystalline,

chloride, polyethylene, polypropylene, polyacrylonitrile, sparingly soluble pigment was then filtered While hot, rubber, casein, silicone and silicone resins, They can also washed with hot ortho-dichlorobenzene, boiling alcohol be used in the manufacture of colored pencils, cosmetic and hot water, and then dried in vacuo at 70 to 80 C. preparations and laminated sheet material. The dyestuff of the formula Compared with the dyestuffs described in German C1 specification No. 1,146,604, which differ from the dyestuffs of the invention in that they contain a Z-hydroxy- 6 C1 3-naphthoic acid-acetylamido-anilide radical instead of a 2 hydroxy 3 naphtholic acid benzoylamino-anilide N (IJONH radical, the dyestufis of the invention exhibit a substan- I tially better fastness to light. i

The following examples illustrate the invention. 0I-I H3O Unless otherwise stated, the parts and percentages are I by Weight. -CONHNHCO- EXAMPLE I I J 103 Parts the y f f h dIaZOUFI'hg f was a red pigment sparingly soluble to insoluble in the chloro 3-am1nobenzo1c acid-(:1 5 common solvents and colored polyvinyl chloride foils aqueous yf lorlc acid soluuon, 1n glacl l ce c 301d bright red tints possessing an excellent fastness to light or with n1trosylsulfuric acid and couphng wrth 2:3- and to migration, hydTOXYIIFIIPhThOhC aclfl Yvsre heated for 3 hours at 120 The azo dyestuif mono-carboxylic acids obtained from t? 1 While shl'rlhg, 3000 P Of Ortho' the binuclear diazo components listed in column I of the (llchlofoheljllene, 5 Ph 0f ylformarnlde and following table and the coupling components listed in Parts of thlohyl Chhmde; F coohhg the reaction column II can be reacted in a manner analogous to that 'f the ntlohocarhoxyhc acld chloflde 0f the dyestuffs described in the first and second paragraphs via the Yvhlch PfeC1Pltated 1n the form thlh, bent needles, Was monoazo dyestufi monocarboxylic acid chlorides with IS l y fihfahoh, Washed Wlth a Small amohht P one mol of the aromatic bi-nuclear monoamines listed in ortho-dihclor-obenzene and benezene and then dried in column III. In column IV are listed the tints of polyvinyl vacuo at to C. chloride foils colored with the pigments.

TABLE I 1 II III IV 1 4-chloro-3-aminobenzoic acid-(2'z5- 2:3-hydroxy-11aphthoic acid 25-dichlor0-4-benzoylaminoaniline Scarlet.

dich1oro)anilide. 2 do do 2:5-dichloro-4-(2';5'-dichloro)-benzoyl- R d,

amino aniline. do 2:fidirnethyl-i-( t chloro)-benzoylamino- Red.

81111118. 2-methoxy-5-ch1oro-4-benzoylalninoaniline- Seal-l ZchIoro-b-methyM-benzoylaminoaniline Red. 2:fi-diniethyl-et-( phenyl)-benzoy1amino Red.

ED11118- 7 4-chloro-3-aminobenzoie acid-(3-trifinoro- 2:3-hydroxy-naphthoic acid 2:5-dichloro-4-benzoylaminoani1ine Scarlet.

methyDanilide. g d d0 2:5-dimethyl-4-benzoylarninoaniline Red, 9 amino-2:4,dichlorobenzoie acid (3-trifiu0rodo 2:5-dimethyl-4-(4-chloro)benzoylamino- Red.

methyD-anilide. aniline. 10 1 .do 2: fi-diehloroi-(4-chloro)benzoylamine- Red.

an e. 2:5-di nethyl-4-benzoylaminobenzoylamino- Bluish red.

1 4- thoxy-3-aminobenzoic acid-(fl-tri- ..do

fluoromethyl)anilide. an ne. 12 do -.d0 .4 2:5'diinethy1'4-(4ph1oro)benzoylamino- D am me. 13 do -.d0 2:5-dimethy1-4-(2:4-dichlor0)-benzoyl- D aminoaniline. 14 do d0 2:5-dich1oro-4-(4'-chloro)benzoylamino- D an: me. 15 do .d 2:5-dimethyl-4-(4 phenyl)benzoylamino- D am me. 16 .-do d 2-chloro-5-methyM-benzoylaminoaniline- D 17 do. t t v 2-meth0xy-5-chloro4-benzoylaminoaniline D 1s 4-methoxy-3-aminobenzoic acid-(3 .....d0 2:5-dichloro4-benzoylaminoaniline ditrifluorornethyl)-anilide. 19 do "d0 2:5-dichloro-4-(4-ch1oro)-benzoy1a1nmo- D am me. 20 do .110 2:adirnethyl-4-benzoylaminoaniline D "do... ..l Mnethoxy-S-ehloro-4-benzoylaminoaniline- Do. -aminobenzoic aci -(2'-eh10rodo 2:5-dichloro-4-benzoylaminoaniline Do. 5-trifluoromethyl)-anilide. D 4 23 do d0 2:5-dimethylA-benzoylaminoanihne D 24 "do" 2methoxy-6-chloro-4-benzoylaminoaniline D 25 d0 2-ehloro-5-methyl-4-benzoylaminoaniline D 26 4-methoxy d0 2:5-dichloro-4-benzoylaminoaniline Do,

dichloro)-anilide. 27 do d0 2:5,1iich1oro-4-(4-ch1oro)-benzoylammo- D am me. 2: fi-dimethyli-benzoylaminoanilinel Do. 2methoxy-5-chloro-4-benzoylarninoaniline. Do. 2;5-dichloro-4-(4-phenyl)-benzoylamino- Do.

aniline. 2:5-dich1or0-4-(4-methy1)-benzoylamino- Do.

aniline. .1 2:5-dimethyl-4-(4'-methoxy)-benzoylar.uino- D0.

aniline. 2-chloro-5-methyl-4-benzoylaminoaniline Do. 34 d0 d0 2:5,dimethyl-4-(4-ehloro)-henzoylamino- Do.

aniline. 35 4-methoxy-3-arninobenzoic aeid-(2:5- -d0 do D trichloro)-anilide. 36 do .-d0 2:5-d1ch10ro-4-benzoylarmnoanilme D TABLE ICntinued I II III IV 37 d0 d0 2:5-dich10r0 4-(4-chl0r0)-benzoylamino- Do.

aniline. 38 do d0 2:5-dimethyl-4-benzoylaminoaniline Do. 1 110.. 2-meth0xy-5-chloro-4-b enzoylamonaniline D o. do 2-chloro-5 methyl-4-benzoylaminoaniline. Do. 41 do. d0 2:S-di neth li-(4-methoxy)-benz0ylamin Bluish.

am 1116. 42..." 4-metl1oxy-3-aminobenzoic acid-3(3-tri- 6-hrom0-2:B-hydroxynaphthoic acid 2;5-dimethyl-4-benzoylaminoaniline Red violet.

fluoromethyD-anilide. 43 do d0 2;5,di nethyll-(y-chlom)-benzoylamino- Do.

8111 I18. 44 4-methoxy-3-aminobenzoic acid-(3-tri- ...do 2z5-dichloro-4-(4-ehloro)benzoylamino- Do.

fluoromethyl)-aniline. aniline. 45 4-methoxy-3-aminobenz0ic acid-(2z4- 2:3-hydr0xynaphth0ic acid d0 ,Bluish r d,

dimeth0xy-5-chl0r0)-anilide. 46 4-methoxy-3-amin0benz01q ac1d-(2z5- d0 2:5dimethyl-4-(4mhlor0)-benzoylamino- Do.

dimethoxy-4-chloro)-an1l1de. aniline.

do 2;5-dirnethyl-4-benzoylaminoaniline-. D0. "do" 2;5-dichloro4-benzoylaminoaniline D0. cl0. 2;5-dicl1loro-4-(4-chloro)-benz0ylamin0ani- D0.

line. 50 5- mino-4-methoxy-2'chlorobenzoic a0id(3- ..d0 2;5-dimethyl-4-benzoylaminoaniline Do.

trifluoromethyD-anilide. 51 do d0 2;5-di nethyl-4-(4 chl0ro)-benzoylamino- Do.

8.111 1118. 52 4-methyl-3-aminobenzoic acid-(3-trifiu0r0- d0 2;5-dimethyl-4-benzoylaminoaniline Do.

methyD-anilide. 53 do d0 2;5-climethyl-4-(4-chlor0)-benzoylamin0- Do.

aniline. I 54 do ..do Z-met110xy-5-ch10I0-4benZOYlaIIllllOflHlllDB-. D0. 55 4-meth0xy3-amin0 zoic acid-(2:5"d1- do 2;5-diinethyl-4'benzoylaminoaniline D0.

methyl-4-chlor0)-anilide. 56 4-methoxy-3-amin0benz0ic acida-napthyl- .do do Do.

amine. 57 4-eth0xy-3-amin0benz0ic acid-(3-trifluoro- .....d0 do Do.

methyD-anilide. I I 53"." 4-methoxy-3-aminobenzoic ac1d-(3-tr1fluoro- ..d0 2;5-diethyl-4-benzoylaminoaniline Do.

methyD-anilide. I I 59 4-(4-ch1oro)-phenoxy-3-ammobenzo1c acid- ..do 2;5-dichloro-4-benzoylaminoaniline Red.

(2: 5-dich10r0ani1ide) 6O .110--. "d 2;5-dimethyl-4-benzoylamin0aniline.. Red. 61 do 1 2-methoxy-5-chloro-4-benzoylaminoan1line Red. 62 4-(4-chloro)-phen0xy-3-am1n0benz010 acldd0 2;5-dimethyl-H)enzoylaminoaniline- Red.

(2:4";5-trich1or0anilide). 63 4- henoxy-3-amin0benz0ic acid (2:5- d0 do Red. dichloroanilide). I I I 64 4-ehlor0-3-amin0benz0i0 ac1d-(3tr1fluor0- -..d0 2:5-dicl1lor0-4(4-chlor0)-benzoylamin0am- Scarlet.

methyD-anilide. line. 65 d0 do Red.

66 .do.. 2-metl1oxy-5-chloroi-benzoylaminoaniline Scarlet. 67"-.- 5-amin02:4di benzoic ac1d-(3-tr fiu d 2;5-dimethyl-4-benzoylaminoaniline Red.

oromethyD-amlide. I I 8". 4-b o 2:5din1ethyl-4-(4-cl1loro)-benzoylaminoani- Red,

romethyD-anilide. I I li e. 69. 4-bromo-3-aminobenzo1c ac1d-(2:5- 2:5-diehloro-4-benzoy1amin0aniline Scarlet.

dichlor0)-anilide. 70 do -d 2:5-dimethyl-4'benz0ylaminoaniline Red. 71 d0 2: 1.S -diLnethyl-l-(4-cl1l0ro)benzoylaminoani Red.

1B8. 72 4-methyl-3-aminobenzoic &cid-(2:5- d0 2;s-dimethyM-benzoylaminoaniline Scarlet.

dichloro)-anilide. 73 2zfi-demethyli-(4-chl0r0)-benzoylaminoani- Red.

1118. 74 do d0 2zg dimethyl--(4-phenyl)-benzoy1aminoan- Red.

1B8. 75 4-methyl-3-aminobenz0ic acid-(2-metl10xyd0 2;5-dimetl1yl-4-(4-ch10ro)-benz0ylamin0an- Red.

5-cl1loro)-anilide. iline. 76 do 0 2'5 dimethyl-4-benzoylaminoaniline Red. 77 do 2. 1 dimethyl-4'(4.-pl1enyl) benzoylaminoan- Red.

line. 78..-" 4-methyl-3-aminobenzoic acid-(2-carb0- .d0 2;5-dimethyl-4-(4-chl0r0)-benz0y1amin0an- Red.

meth0xy-5-chlor0)-anilide. iline. 79-.. 4-methyl-3-aminobenz0ic acid-(2z z54i .--..d0 2;5-dichloro-4-(4-chloro)-benzoylaminoan- Red.

chloro)-anilide. iline. 8O do (1 2:3:dimethyl-4r(4-ch1or0)-benzoylaminoan- Red.

1 H18. 81 d0 d0 2;:dimethyl-4-(4'-pheny1)-benz0ylamin0an- Red.

me. 82 4-methyl-3-amin0benzoic acid-(3-trifl 0r0- ..d0 2;5-dimethyl-4benzoylaminoaniline Red.

methyD-anilide. 83 do ..d 2-metl1oxy-5-chloro-4-benzoylaminoaniline. Red. 84. 4-me 0 y- Monobenzoyl-p-phenylenediamine Bluish red.

romethyl anilide. I s5 4-ethctJxyi3-aminobenz0ic acie-(3-tr1flu0r0- do do Do.

me by 86 4-methoxy-3-amin0benz0ic acid-(3-trifl110 0- .-d0 4-(4-chl0ro)-benz0ylamino-aniline Do.

methyl anilide. I I 87..- 4-methyl-3-aminobenzoic acid-(2-ch10r0- d0 M0110benzoyl-p-phenylenediamine Red.

trifluoromethyD-anilide. I 88.-. 4-chloro-3-aminobenzoic ac1d-(3-tnflu0r ....-d0 4-(4-chlor0)-benzoylaminoaniline Red.

methyD-anilide. 89. do --d0 4-(4-methoxy)-benzoylaminoaniline Orange.

h10r0-i3)-amli}gb8DZ0l0 acid-(3-tr1flu0r0- -...d0 4-(4-phenyl)-benzoylaminoaniline Red.

y -ani1 e. d0 4-(4-metl1yl)-benzoylaminoaniline Scarlet. I -do 4-(4'-carbomethoxy-benzoylamino-aniline Orange. ymen I 010 ac1d-(2-chl0r0- .....d0 Mon0benzoyl-p-phenylenediamine Bluish red. tritlu0ron1ethyl)-an1l1de. 94 d0 d0 4-(4-metl1y1)-benzoy1aminoaniline Do. 95 4-methoxy-3-aminobenzoic ac1d-(3,5-d1 r1- .d0. Monobenzoyl-p-phenylenediamine Do.

fluoromethyD-anihne. I 96"-.. 4-methyl-3-aminobenzoic ac1d-(2,4,5- r1- d0 4-(4-phenyl)-benzoylaminoaniline Red.

chloro)-anilide. I I I 97.. 4-methyl-3-aminobenzoic ac1d-(3-tr1fiu0r .d M0nobenzoyl-p-phenylenediamine Red.

methyD-anilide.

98 do --d0 4-(4-methoxy)-benzoylaminoaniline Red. 99 do 4-(4-chl0r0)-benzoylamin0aniline Red.

TABLE 'I Continued I II III IV 100.... 4-methy1-3-aminobenzoic acid-(5-chlor0-2- do Monobenzoyl-p-phenylenediamine Red.

methoxy)-anilide. 101-... 4-methoxy-3-an1inobenzoic acid'(3-trifluorodo 2,5-dimethoxy-4-(4-chloro)-benzoylamino- Bluish red.

methyD-amhde. aniline. 102.-.. 4-methyl-3-amin0beuzoic acid-(5-carbodo -do Red.

methoxy-2-chloro)-anilide. 103.-.. -methoxy-B-aminobenzoic acid-(3-trifluor0- do 4-benzoylamino-S-methylaniline Bluish red.

methyD-anilide. 104 .do do 2,5-dirnethoxy-4-(4-acetylamin0)-benzoyl- D aminoaniline. 105 ..do do 4-(4 phenyl)-benzoylamino-3 methoxy- D0.

amine. 106 -do -do 'me%hy1-Z-methoxy-4-benzoylamino- Do.

am me. 107 --d0.. do 2,5-diiqhloro-l-(2,4-dimethyl)-benzoylamino- Do.

am me. 108.-.. 4-chloro-3-aminobenzoic aeid-(2-5-diohlor0)- do 4-(4-methoxy)jbenzoylamino-2-meth0xy- Scarlet.

anilide. aniline.

....................... do 2,fi-dimethoxyA-W-chloro)-benz0ylam1n0- Do.

aniline. do. 4-benzoylamino-2-methylaniline...- D0. rd minobenzoic acid-(3"eh10r0)- do 2,5-dichloro-4-benzoylaminoaniline Red. 31111 8. 112.-.. 4-methoxy-3-aminnbenzoic acid-(3-triflu01'0- do 2-methyl-4-(4-methoxy)-benz0ylamino Red.

methyD-anilide. aniline. I 113.-.. 4-metl1oxy-3-aminobenzoic aeid-(3-carb0- do 2-methoxy-5-ehloro-4-benzoylaminoaniline. Bluish red.

methoxy)-anilide.. 114.... 4-6-dichloro3'aminobenzoic acid-(2,4- do Monobenzoyl-p-phenylenediamine Scarlet.

dichloro)-anilide. 115.-.. 4-metlliloig-3-afniinobenzoic acid-(3'-tr1flu0r0- do 3-methyl-4-benzoylaminoaniline Bluish red.

met y -anii e. 116--.. 4-chloro-3-aminobenzoic acid-(2,5-dido 2-methoxy-4-(4-n1ethoxy)-benzoylamino- Scarlet.

chloro)-anilide. anilide. 117-... 4-111ethylmercapto-fi-aminobenzoic aciddo M0nobenzoyl-p-phenylenediamme Bluish red.

(3- ifluoromethyD-anilide. H 118 .do do 2,5-dimethy1-4-benzoylaminoaniline D0. 119 .-do do 2,5-d i11 nethyl-4-(4-phenyl)-benz0yl-amino- Do.

am 1H6- 120-.-. 4-(4-chloro)-phenoxy-3-aminobenzoic aeiddo 2,5-dimethyl-4-benzoylaminoanilide Red.

(2,5-dichloro)-anilide. 121.... 4-(4-chloro)-phenoxy-3-aminobenzoi0 aciddo Monobenzoyl-p-phenylenediamine Scarlet.

(3-trifluoromethyl)-anilide. 4 122.--. 4-chloro-3'aminobenzoic aoid(2,4'-dld0 do D0.

chloro)-anilide. do..-. .l. 4-(4-chloro-benzoylaminoamline..--- Orange 124.... 4-methyl-3-aminobenzoic acid-(2,4-dichl0ro--. d0 Monobenzoyl-p-phenylenediamine Red.

chl0ro)'ani1ide. I 125.... 4-chloro-3-aminobenzoic acid-(2,4-d1- do 2,5-d1methyl-4-benz0y1amin0aniline.. Red.

chr0)-ani1ide. 126.... 4methyl-3-aminobenzoic acid (3-trifluorodo 4-(4-metl1y1)-benz0y1a1n1noan1l1ne-. Red.

methyD-anilide 127.-.. 4-chloro-3-aminobenzoic acid-(3-trifluorodo 4-(4-carbon1ethoxy)-benzoylammoanil1ne.-.- Orange.

methyD-anilide. 128.--. 4-ch1oro-3-aminobenzoic acid-(2,5-dido 4-(4-phenyl)-benzoy1an1moan1l1ne Red.

ch10ro)-anil1de.

EXAMPLE 2 11.8 parts of 4-methoxy-3-aminobenzoic acid-(3'-trifluoromethyD-anilide were suspended in 100 parts of glacial acetic acid, 12 parts of 30% hydrochloric acid were added to the suspension and diazotisation was carried out at 0 to 5 C. with 11.2 parts of 4 N sodium nitrite solution. After 30 minutes, the mixture was diluted with 150 parts of ice water, filtered, and the clear diazo solution added to a solution of 17 parts of l-dimethylaminomethyl 2 hydroxy 3 naphthoic acid (4'- benzoylamiuo-Z':5'-dimethyl)-phenylamide in 1500 parts of water and 22 parts of 2 N hydrochloric acid at 10 to C. The mixture was then bufiered to a pH-value of 4.5 to 5 with sodium acetate solution and stirred for 14 hours at 10 to C. After suction filtration and washing with water, the filter cake was suspended in 110 parts of 5 N hydrochloric acid, the suspension stirred for 1 hour at room temperature, filtered, and the filter residue washed with dilute hydrochloric acid and Water. The pigment was treated for 2 hours on a boiling water bath with 300 parts of pyridine, filtered while hot, washed with pyridine, ethanol and hot water and then dried in vacuo at 70 to 80 C. A dark red, soft-grained-powder was obtained which was very sparingly soluble in organic solvents and, when worked into polyvinyl chloride foils, produced a brilliant bluish red tint possessing a very good fastness to migration and to light.

The pigment so obtained, which corresponded to No. 12 of the Table I, had the following formula benzoic acid-(2: 5- dichloro)-anilide.

11 EXAMPLE 3 23.3 parts of 4-methoxy-3-arninobenzoic acid(3'-trifluoromet-hylanilide) were dissolved in 45 parts of warm glacial acetic acid, the solution so obtaine was allowed to run into a solution of 30 parts of 30% hydrochloric acid, while stirring, and the mixture diazotised at to 5 C. with parts of 4 N sodium nitrite solution and then filtered until clear.

32.3 parts of 2-hydroxy-3-naphthoic acid-(4'-benzoylamino-2:5-dimethylphenyl)-amide were dissolved in a cold mixture comprising 80 parts of ethyleneglycol monoethyl ether and 66 parts of sodium hydroxide solution. The tWo solutions, if necessary diluted with water, were conveyed continuously to a mixing nozzle, where immediate coupling of the components took place. The pH-value in the mixing nozzle was kept between 5 and 6 by regulating the supply of the solutions and the temperature was held between and C. This could be regulated by the addition of water to the solutions of the components. The resulting dyestuff suspension was filtered and the filter residue, after washing, was stirred in a mixture comprising 20 parts of water, 110 parts of ethyleneglycol monoethyl ether and 100 parts of orthodichlorobenzene, and the whole then filtered. The filter residue was washed successively with ethyleneglycol monoethyl ether and methanol and then dried in vacuo at to 80 C. The dyestuff, which was obtained in almost quantitative yield, corresponded in respect of tint, purity, fine state of division and fastness properties, to the product obtained in accordance with Example 1 (dyestuif No. 12 of Table I). The dyestufi is obtained in a particularly good state of fine division when the solution of the diazo component or of the coupling component contains an anionic or nonionic wetting agent, for example, the sodium salt of N-benzyl- -heptadecylbenzirnidazole-disulfonic acid. What is claimed is: 1. An azo-dyestuff of the formula l CONHQ Z1 Yr in which X represents a member selected from the group consisting of hydrogen and bromine, X a member selected from the group consisting of chlorine and trifiuoromethyl, Y and Z members selected from the group consisting of hydrogen, chlorine and trifiuoromethyl, Z a member selected from the group consisting of chlorine, lower alkyl, lower alkoxy, and lower alkylmercapto Z a member selected from the group consisting of hydrogen and chlorine, X and Y are members selected from the group consisting of hydrogen chlorine, lower alkyl, and lower alkoxy X a member selected from the group consisting of chlorine, lower alkyl, lower alkoxy, lower carbalkoxy, lower alkanoylamino and phenyl, and n is a Whole number from 1 to 3.

2. The dyestuif as claimed in claim 1 of the formula 3. The dyestuff as claimed in claim 1 of the formula 4. The dyestuff as claimed in claim 1 of the formula II I N CONHQ --NHC oQ-cooorn 5. The dyestufi? as claimed in claim 1 of the formula CONTI- 6. The dye stuff as claimed in claim 1 of the formula 7. The dyestuff as claimed in claim 1 of the formula (I) CH I I I 8. The dyestufi as claimed in claim 1 of the formula II I N I o ONH- References Cited UNITED STATES PATENTS 3,219,655 11/1965 Ranco 260203 CHARLES B. PARKER, Primary Examiner.

D. M. PAPUGA, Assistant Examiner. 

1. AN AZO-DYESTUFF OF THE FORMULA 